Journal of Colloid and Interface Science最新文献

The development of facile and scalable methods to fabricate green photocatalysts with efficient charge separation remain pivotal for advancing photocatalytic H₂O₂ production toward practical applications. Herein, a sulfonic acid-functionalized benzoxazine-based phenolic resin (SAPFac) was reported for in situ H₂O₂ production and utilization. The electron-withdrawing sulfonic groups (-SO₃H) induce a robust intramolecular built-in electric field and impart surface negative charges, thereby synergistically enhancing photogenerated carrier separation efficiency and optimizing proton/oxygen affinity. The sulfonic acid-linked benzene rings in SAPFac serve as electron-enrichment centers, lowering the energy barrier for *OOH intermediate formation to favor the 2e^- oxygen reduction reaction (ORR) pathway to generate H₂O₂. Consequently, this molecular engineering strategy endows SAPFac resins with an exceptional H₂O₂ production rate of 4410.9 μmol g^-1 h^-1 under visible light without sacrificial agents or oxygen aeration, which is 2.1 times of pristine benzoxazine-based phenolic resin (APFac). Coupled with Fe³⁺, photo-self-Fenton system was constructed to achieve rapid degradation of antibiotics and complete inactivation of high-density antibiotic-resistant bacteria (∼10⁷ CFU/mL) via in situ activation of H₂O₂ into hydroxyl radicals (•OH). This work establishes a green and sustainable paradigm for polymer photocatalyst design, promoting the development of real field implementation of solar-driven H₂O₂ synthesis technology.

Antimony sulfoiodide (SbSI) and antimony selenoiodide (SbSeI) are well-known chalcohalides extensively used in electronic and optoelectronic applications; however, their potential for photocatalytic CO₂ reduction has not been previously explored. In this study, both SbSI and SbSeI demonstrated effective triple functionality-converting CO₂ into hydrocarbons and H₂ evolution, while simultaneously degrading crystal violet (CV) under visible-light irradiation. After optimization, the SbSI catalyst achieved a CH₄ yield of 1340.2 ppm and an H₂ yield of 7533.8 ppm, while SbSeI produced 1244.8 ppm of CH₄ and 8917.4 ppm of H₂. The main reaction products were hydrocarbons and H₂, with high selectivity toward methane: 85.8% CH₄ and 14.2% C₂⁺ for SbSI, and 84.2% CH₄ and 15.8% C₂⁺ for SbSeI, respectively. This indicates a sequential conversion pathway from CO₂ to CH₄, followed by CC coupling to form higher hydrocarbons. Additionally, both catalysts showed excellent photocatalytic activity for the degradation of CV dye, with apparent rate constants (k) of 0.1679 h^-1 for SbSI and 0.0554 h^-1 for SbSeI. These results highlight the dual photocatalytic capability of Sb-based chalcohalides, providing new insights into their application in CO₂-to-hydrocarbon conversion and environmental remediation, thereby contributing to sustainable chemical and energy systems.

Photosynthesis for H₂O₂ production and pollutant degradation is a promising strategy to solve energy shortages and environmental pollution. However, developing photocatalysts with high-efficiency charge separation, migration, and utilization remains a major challenge. Herein, an organic-inorganic S-scheme heterojunction was constructed by integrating a Schiff-base covalent organic framework (COF) with CdIn₂S₄ (CIS). Leveraging the staggered energy band alignment and work function difference between COF and CIS, a built-in electric field (IEF) was established at their interface, which not only enabled rapid interfacial charge transfer but also preserved sufficient redox potentials, thereby achieving enhanced photocatalytic activity. The optimized COF/CIS heterojunction leverages its hierarchical structure, broad visible-light absorption, and efficient S-scheme charge transfer to achieve a high photocatalytic H₂O₂ generation rate of 3247 μmol·g^-1·h^-1 in RhB solution (10 mg·L^-1). An apparent quantum yield (AQY) of 3.87% is attained under 420 nm monochromatic light irradiation, along with a RhB degradation efficiency of approximately 93.2%. Furthermore, the enhanced interfacial charge transfer via the S-scheme heterojunction is elucidated using in-situ irradiated X-ray photoelectron survey spectrum (ISI-XPS) and femtosecond transient absorption (fs-TA) spectroscopy. This work establishes a rational design strategy for IEF regulation in organic-inorganic S-scheme heterojunction photocatalysts, thereby advancing the new prospects for artificial photosynthesis in energy and environmental applications.

Composite solid electrolytes (CSEs) based on garnet Li₇La₃Zr₂O₁₂ (LLZO) are promising for solid-state batteries due to high ionic conductivity and flexibility. However, interfacial instability with lithium metal anodes promotes dendrite growth and side reactions. To address this issue, an in situ polymerized interfacial layer (TPELL layer) was constructed by copolymerizing trimethyl phosphate (TMP) and ethylene carbonate (EC) between the Li anode and CSE. The copolymerization of EC and TMP effectively regulates the solvent structure within the interfacial layer, which in turn modulates the Li⁺ coordination environment and enhances the mechanical robustness of the interface. Furthermore, the incorporation of EC and LiPF₆ promotes the formation of a more stable lithium metal anode/electrolyte interface. Consequently, the Li||LiFePO₄ battery with CSE containing interfacial layer formed by copolymerization of TMP and EC exhibits a capacity retention of 93.83 % after 750 cycles at 1C and the Li||LiNi_0.8Co_0.1Mn_0.1O₂ battery maintains 130.1 mAh g^-1 after 350 cycles at 0.5C. Post-cycling analysis indicates that the preserved integrity of the cathode structure can be ascribed to the formation of a multifunctional cathode electrolyte interphase (CEI) derived from TPELL components, which effectively suppresses transition-metal dissolution and alleviates interfacial resistance. Moreover, this in situ polymerization strategy facilitates intimate interfacial contact at both the anode and cathode, thereby providing a promising pathway to address the persistent electrode/electrolyte interfacial challenges in solid-state lithium metal batteries.

To address the critical challenge of balancing structural stability and high capacity in vanadium-based cathodes for aqueous zinc-ion batteries (ZIBs), we propose a rational design strategy based on the structural coupling of Mg-intercalated bilayer V₂O₅ (MVO) and monolayer V₂O₅, collectively referred to as C-MVO. The C-MVO cathode is synthesized through a facile Polytetrafluoroethylene (PTFE) assisted sonochemical approach followed by controlled thermal annealing. This unique architecture synergistically integrates enhanced stability of MVO with abundant active sites of V₂O₅. The C-MVO cathode achieves a high capacity of 518.9 mAh g^-1 (0.1 A g^-1), with 89.2% retention after 1000 cycles (1.0 A g^-1). Comprehensive interfacial kinetic analysis reveals significantly reduced activation energy barriers for Zn²⁺ desolvation at the solid-liquid interface (55.7 kJ mol^-1) and solid-state diffusion (19.2-24.4 kJ mol^-1) compared to pristine V₂O₅. Ex-situ characterizations confirm highly reversible Zn²⁺ (de)intercalation and robust structural integrity. This work establishes a paradigm for designing high-stability, high-capacity ZIB cathodes through targeted structural hybridization, coupled with a scalable and energy-efficient synthesis route, paving the way for practical applications.

Nano zero-valent iron (nZVI)-based advanced oxidation processes (AOPs) have broad application prospects in environmental remediation, but the surface passivation of nZVI severely limits their performance. Although carbon coating can inhibit the oxidative passivation of nZVI in air, the deposition of iron ions on its surface during the reaction still leads to its rapid deactivation. In this study, crystalline boron was introduced as a novel co-catalyst to activate peroxydisulfate (PDS) in conjunction with carbon-coated nZVI (Fe⁰@C) for the degradation of tetracycline (TC). The results showed that the Boron/Fe⁰@C/PDS system achieved complete removal of TC within 1 min. Free radical scavenging and chemical probe experiments confirmed the generation of multiple reactive oxygen species, with singlet oxygen being primarily responsible for the degradation of TC. Mechanism investigations revealed that crystalline boron can accelerate the redox cycle of iron ions by donating electrons, thereby inhibiting the deposition of iron ions on the Fe⁰@C surface and achieving the stable release of ferrous ions and the continuous activation of PDS. Furthermore, crystalline boron gradually undergoes surface oxidation during the electron donation process, but its surface self-cleaning effect can continuously expose new active sites. The synergistic effect of crystalline boron and carbon coating prevents passivation of nZVI throughout its lifecycle, thereby ensuring excellent catalytic efficiency and long-term stability. This study provides a practical anti-passivation strategy and offers new insights into the rational design of nZVI-based AOPs.

Hard carbon (HC) is the most promising commercially available anode material for sodium-ion batteries (SIBs) due to the high specific capacity, low operation voltage and low cost. However, HC faces the problems of poor initial Coulombic efficiency (ICE) and ambiguous sodium storage mechanism. Furthermore, the relationship between solid electrolyte interphase (SEI) characteristics, particularly its chemical composition and microstructural features, and electrochemical performance remains poorly understood. To this end, HC with abundant closed pores and adjustable defect concentration was prepared in this study using cheap pine bark as raw material through precise thermal regulation. At high pyrolysis temperature, the carbon layer in HC fully grows and promotes the growth of closed pore. The optimized PHC-1300 exhibits a high ICE of 89.6% and an outstanding specific capacity of 347.62 mAh g^-1 at 0.1C. Moreover, the PHC-1300//Na₃V₂ (PO₄)₃ full-cells also exhibit excellent cycling performance. Based on the electrochemical performance and microstructure of the pine bark-based HC, it is proposed that the sodium storage mechanism is "adsorption-intercalation-filling". Notably, it is found that the HC surface with suitable defect concentration can induce the formation of fluorine-rich organic SEI phase, which is beneficial to maintain the interfacial stable to improve the cycling stability.

Solvent coordination structures, including contact ion pairs (CIPs), aggregates (AGGs) and solvent-separated ion pairs (SSIPs) in solid polymer electrolytes (SPEs) are considered to profoundly affect the ionic conductivity and formation of stable solid electrolyte interphase (SEI). The significance of individual effect of SSIPs has been neglected although numerous studies have focused on investigating their collaborative impact on the SEI by regulating the proportion of solvent coordination structures. Here, this work intends to study the unique effect of SSIPs by tailoring the concentration of SSIPs from 0 % to 2.8 % through introducing vinylene carbonate (VC). The comprehensive analysis based on experiments and theoretical calculations indicates that the SSIPs induced by strong competitive coordination effect is beneficial to promote fast Li⁺ ion transport and facilitate the formation of an organic/inorganic composite SEI. Moreover, a highly stable electrochemical interface is achieved by constructing a uniformly distributed lithium fluoride (LiF) SEI. Specifically, stable cycling of Li||Li symmetric cells for 1200 h is demonstrated at a current density of 0.1 mA cm^-2. Additionally, Li||LFP cells exhibit 550 stable cycles at 0.5C, with an average coulombic efficiency exceeding 99.9 % and a capacity retention of 96.5 %. This strategy independently investigates the role of SSIPs in SPEs and offers a new approach for further research on advanced lithium metal batteries.

Lack of double-high (high energy density and power density) anode materials is the key bottleneck for the application of Aqueous alkaline batteries (AABs). Although the emergence of Bismuth-based materials provides an opportunity to solve this issue, due to their high theoretical capacity via a three-electron redox reaction and suitable operating potential, their restricted ion diffusion kinetics via closed-packed atomic arrangement limit their application performance. Herein, the bismuth oxyfluoride hollow nanorods (BiOF-HNs) with intrinsic layer atom configuration have been constructed by the crystallization optimization and morphology engineering synergistic strategy during MOF etching process. Bi³⁺ hydrolysis is the key points to achieve the co-precipitating and repining reactions of BiOF at the surface of Bi MOF for hollow nanorods morphology. The BiOF-HNs deliver dramatically increased electron conductivity and ion transport ratio with the work function of 6.42 eV and OH^- diffusion value of 2.11 × 10^-13 cm² s^-1. Therefore, the optimized BiOF-HNs electrode delivers a remarkable specific capacity of 342.2 mAh g^-1 (1232 F g^-1) at 1 A g^-1 and maintains 86% capacity retention at 20 A g^-1. Furthermore, the assembled BCNP (basic cobalt/nickel phosphate)//BiOF-HNs AABs achieve a high energy density of 157.81 Wh kg^-1 at 1.28 kW kg^-1 and outstanding cycling stability (81% after 9000 cycles). The exploration of BiOF materials with morphology and crystalline optimization in AABs application, may offer new insights of design high performance aqueous anode materials.

Mass transfer limitations directly govern the utilization efficiency of active sites in gas-involving reactions, thereby hindering intrinsically active sites from functioning effectively at high current densities. Consequently, designing porous structures to improve the transport efficiency of both reactants and products constitutes a central challenge for realizing efficient and stable electrocatalytic processes. To address this challenge, a nickel‑cobalt (NiCo) alloy was fabricated via digital light processing (DLP) technology, and cobalt-nanocarbon (Co NC) active material was incorporated in situ to establish a robust catalytic system. Furthermore, the deliberate structural design promoted bubble mass-transfer kinetics, thereby further improving its performance across multiple catalytic reactions. The electrolysis water device composed of it can operate stably for over 500 h at a current density of 500 mA cm^-2 and a voltage of 1.78 V. The assembled zinc-air battery shows a peak power density of 73.5 mW cm^-2 and outstanding cyclic durability, lasting for over 300 h. More importantly, the assembled integrated device generates an equivalent amount of hydrogen during both day and night. This innovative strategy offers a reliable reference for the practical implementation of three-dimensional electrodes in highly efficient mass transfer reactions.